A new strategy was developed for the synthesis of well-defined eight-shaped polymethylene (PM, equivalent to polyethylene) -based cyclic block copolymers, [c-(PM-b-PCL)](2), according to the following four steps: (a) synthesis of a B-thexyl-boracyclic initiator by cyclic hydroboration of 1,4-pentadiene-3-yl 2,2,5-trimethyl-1,3-dioxane-5-carboxylate with thexylborane; (b) polyhomologation of dimethylsulfoxonium methylide using this boracyclic initiator to afford alpha,omega-dihydroxyl linear PM (PM-OH)(2); (c) synthesis of 4-miktoarm star block copolymers, (PM-alkyne)(2)-(PCL-N-3)(2), by esterification, deprotection, and ring-opening polymerization (ROP); and (d) intramolecular cyclization of (PM-alkyne)(2)-(PCL-N-3)(2), under high-dilution condition by copper-catalyzed "click" chemistry. All intermediates and final products were characterized by high -temperature gel permeation chromatography, proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and differential scanning calorimetry. Initial studies on the thermal and self-assembly behavior of the cyclic block copolymers and their corresponding precursors revealed a significant influence of the cyclic structure on the properties.